Multifunctional curing agents and their use in improving strength of composites containing carbon fibers embedded in polymeric matrix

ABSTRACT

A functionalized carbon fiber having covalently bound on its surface a sizing agent containing epoxy groups, at least some of which are engaged in covalent bonds with crosslinking molecules, wherein each of said crosslinking molecules possesses at least two epoxy-reactive groups and at least one free functional group reactive with functional groups of a polymer matrix in which the carbon fiber is to be incorporated, wherein at least a portion of said cros slinking molecules are engaged, via at least two of their epoxy-reactive groups, in crosslinking bonds between at least two epoxy groups of the sizing agent. Composites comprised of these functionalized carbon fibers embedded in a polymeric matrix are also described. Methods for producing the functionalized carbon fibers and composites thereof are also described.

This invention was made with government support under prime contract No.DE-AC05-00OR22725 awarded by the U.S. Department of Energy. Thegovernment has certain rights in the invention.

FIELD OF THE INVENTION

The present invention relates, generally, to composites made of carbonfibers and a polymeric matrix, and also to the use of sizing agents inorder to modify the interfacial interactions between two phases of asolid composite.

BACKGROUND OF THE INVENTION

Carbon fiber reinforced composites are known for their outstandingmechanical properties associated with a low density. Some of thoseoutstanding mechanical properties include superior tensile, flexural,and shear properties and impact resistance. For this reason, they havebeen of interest to many fields, particularly for rugged applications,such as the space and aeronautics industries, military equipment,transportation, and infrastructure.

Carbon fiber-epoxy composites are particularly used in such ruggedapplications. Although there has been a desire to extend the applicationof carbon fiber-epoxy composites to more commonplace markets, such asthe automotive industry, tools, appliances, and sporting andrecreational goods, their extension into these other markets has beensubstantially impeded by the higher cost of high performance epoxyresins relative to other resin systems. Less costly substitutes of epoxyresin have been sought, but the mechanical properties of thesesubstitutes have thus far not approached the outstanding mechanicalproperties provided by high performance epoxy resins.

Vinyl ester resins are less costly than high performance epoxy resins,and are widely used, particularly because of their high resistance tomoisture absorption and corrosion. Thus, vinyl ester resins would be ahighly desirable substitute for an epoxy resin if only the resultingcarbon fiber-vinyl ester resin composite could approach the outstandingmechanical properties provided by epoxy resin-based composites. However,the mechanical properties of carbon fiber-vinyl ester composites cannotcurrently compete with the mechanical properties of carbon fiber-epoxycomposites. For this reason, carbon fiber-vinyl ester resin compositeshave not been considered for applications in which outstandingmechanical properties (e.g., high strength and ruggedness) are required.

The physico-chemical and mechanical properties of a composite materialare not only dependent on the characteristics of the reinforcementmaterial and the matrix, but also largely dependent on the properties ofthe interface. If the fiber-matrix interface is weak, the structuralintegrity of the composite material will be compromised. Moreover,unlike high performance epoxy resins, and particularly in the case of avinyl ester resin matrix, a high cure volume shrinkage can furtherdiminish the integrity of the fiber-matrix interface. Thus,methodologies for improving a fiber-matrix interface in an epoxy matrixare generally not applicable for a vinyl ester resin or other type ofmatrix. For this reason, vinyl ester resin composites have been largelyunconsidered for rugged applications, although vinyl ester resins areless costly than high performance epoxy resins. Hence, a great benefitwould be provided by a methodology that could significantly strengthenthe fiber-matrix interface in composites containing any of a variety ofpolymeric matrix materials, including vinyl ester resins, unsaturatedpolyester resins, vinyl addition polymers, and more.

SUMMARY OF THE INVENTION

In one aspect, the invention is directed to a carbon fiber havingcovalently bound on its surface a sizing agent containing epoxy groups,at least some of which are engaged in covalent bonds with crosslinkingmolecules. The crosslinking molecules possess reactive groups thatfunction to crosslink between epoxy groups in the sizing agent and alsofunction to crosslink between the sizing agent and a polymer matrix. Toaccomplish this, each of the crosslinking molecules possesses at leasttwo epoxy-reactive groups and at least one free functional groupreactive with functional groups of a polymer matrix in which the carbonfiber is to be incorporated. At least a portion of the cros slinkingmolecules are engaged, via at least two of their epoxy-reactive groups,in crosslinking bonds between at least two epoxy groups of the sizingagent.

In another aspect, the invention is directed to a solid composite inwhich the above-described functionalized carbon fibers are embedded in apolymeric matrix. The polymeric matrix can be a thermoset orthermoplastic polymer, or more particularly, a vinyl ester resin or anunsaturated polyester resin. In the composite, the at least one freefunctional group in the crosslinking molecules is crosslinked withfunctional groups of the polymer matrix. The invention is also directedto a device or apparatus that contains the composite, such as aprotective or impact-resistant layer, coating, or film, or an interioror exterior siding or surface of a structure, such as an automobile,aircraft, or building, or a tool or appliance, particularly where alightweight high-strength material is desired.

In yet another aspect, the invention is directed to a method of making afunctionalized carbon fiber having on its surface an at least partiallycured sizing agent containing epoxy groups. Generally, the methodincludes covalently binding on the surface of a carbon fiber a sizingagent containing an epoxy resin, and at least partially curing thesizing agent by contact thereof with a crosslinking molecule possessingat least two epoxy-reactive groups and at least one free functionalgroup reactive with functional groups of a polymer matrix in which thecarbon fiber is to be incorporated. After the at least partial curingstep, at least a portion of the cros slinking molecules are engaged, viaat least two of their epoxy-reactive groups, in crosslinking bondsbetween at least two epoxy groups of the sizing agent. The at least onefree functional group in the crosslinking molecule remains available forsubsequent crosslinking with reactive groups of the polymeric matrix. Inthe method, the at least partial curing step is performed on the sizingagent before or after the sizing agent is covalently bound to thesurface of said carbon fiber.

In still another aspect, the invention is directed to a method of makingthe solid composite described above. The method includes admixingfunctionalized carbon fibers (i.e., functionalized with an at leastpartially cured sizing agent), described above, with a polymer precursorresin, and curing the polymer precursor resin to form a cured polymericmatrix that contains the functionalized carbon fibers embedded therein.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1A, 1B. For FIG. 1A: Schematic of a first exemplary embodiment inwhich crosslinking molecules bearing at least two epoxy-reactive groups(e.g., isocyanate groups) and at least one matrix-reactive functionalgroup (depicted by solid circle) are crosslinked with an epoxy sizing ona carbon fiber to provide at least one matrix-reactive functional groupon the sizing free and available for subsequent reaction with aprecursor polymer matrix. For FIG. 1B: Analogous to the scheme shown inFIG. 1A, except that the crosslinking molecule possesses allepoxy-reactive groups, with at least two epoxy-reactive groups formingcrosslinking bonds with the epoxy sizing, and at least oneepoxy-reactive group forming a crosslinking bond with a precursorpolymer matrix.

FIG. 2. Schematic of a second exemplary embodiment in which crosslinkingmolecules bearing at least two epoxy-reactive groups (e.g., isocyanategroups) and at least one matrix-reactive functional group (depicted bysolid circle) are crosslinked with an epoxy sizing on a carbon fiber toprovide at least one matrix-reactive functional group on the sizing freeand available for subsequent reaction with a precursor polymer matrix inaddition to at least one free epoxy-reactive group on the sizing thatcan function to form an additional cros slinking bond with the precursorpolymer matrix.

DETAILED DESCRIPTION OF THE INVENTION

The carbon fiber can be any of the high strength carbon fibercompositions known in the art. As known in the art, the carbon fiber hasits length dimension longer than its width dimension. Some examples ofcarbon fiber compositions include those produced by the pyrolysis ofpolyacrylonitrile (PAN), viscose, rayon, pitch, lignin, polyolefins, aswell as vapor grown carbon nanofibers, single-walled and multi-walledcarbon nanotubes, any of which may or may not be heteroatom-doped, suchas with nitrogen, boron, oxygen, sulfur, or phosphorus. The inventionalso applies to two-dimensional carbon materials, e.g., graphene,graphene oxide, graphene nanoribbons, which may be derived from, forexample, natural graphite, carbon fibers, carbon nanofibers, singlewalled carbon nanotubes and multi-walled carbon nanotubes. The carbonfiber considered herein generally possesses a high tensile strength,such as at least 500, 1000, 2000, 3000, 5000, 10,000 or 20,000 MPa, witha degree of stiffness preferably of the order of steel or higher (e.g.,100-1000 GPa).

For purposes of the instant invention, the carbon fibers preferably haveepoxy-reactive groups on their surfaces engaged in covalent bonds withthe epoxy-containing sizing agent. Some examples of epoxy-reactivegroups include hydroxyl (OH), carboxyl (COOH), and amino (e.g., NH₂)groups, any of which can be on the surface of the carbon fiber. Carbonfibers can be surface-functionalized with such reactive groups bymethods well known in the art, such as by an oxidative surfacetreatment. Moreover, such surface-functionalized carbon fibers are alsocommercially available.

Preferably, the epoxy resin covalently bound to the carbon fiber surfacepossesses at least two epoxide (epoxy) groups (i.e., prior to bindingand crosslinking), and thus, can be a difunctional, trifunctional,tetrafunctional, or a higher functional epoxy resin. When covalentlybound to the carbon fiber, the epoxy resin is bound via a portion of itsepoxy groups, with a portion of epoxy groups available for furtherreaction (e.g., crosslinking). In some embodiments, the epoxide group ispresent as a glycidyl group. The epoxy resin (i.e., before covalentbonding to the carbon fiber or crosslinking) can be convenientlyexpressed by the following generic structure:

In Formula (1), n is precisely or at least 1, 2, 3, 4, 5, 6, or anysuitable number, including a higher number (e.g., 10, 20, 30, 40, or 50)typical for a polymer having epoxide-containing units. The group R is asaturated or unsaturated hydrocarbon linking group having at least oneand up to any suitable number of carbon atoms. In different embodiments,R can have precisely or at least, for example, 1, 2, 3, 4, 5, 6, 7, 8,9, 10, 12, 15, 18, 20, 25, 30, 35, 40, or 50 carbon atoms, or a numberof carbon atoms within a range bounded by any two of these values. Someexamples of saturated hydrocarbon groups suitable as R includestraight-chained or branched alkylene groups or cycloalkylene groups,such as methylene (i.e., —CH₂—), ethylene (i.e., —CH₂CH₂—), n-propylene(i.e., —CH₂CH₂CH₂—, or “trimethylene”), isopropylene (—CH(CH₃)CH₂—),tetramethylene, pentamethylene, hexamethylene, —C(CH₃)₂CH₂—,—CH(CH₃)CH(CH₃)—, —CH₂C(CH₃)₂CH₂—, cyclopropylene (i.e.,cyclopropyldiyl), 1,3-cyclobutylene, 1,2-cyclopentylene,1,3-cyclopentylene, 1,2-cyclohexylene, 1,3-cyclohexylene, and1,4-cyclohexylene. Some examples of unsaturated hydrocarbon groupshaving 1 to 4 carbon atoms include straight-chained or branchedalkenylene or alkynylene groups or cycloalkenylene groups, such asvinylene (—CH═CH—), allylene (—CH₂-CH═CH—), —CH₂-CH₂—CH═CH—,—CH₂-CH═CH—CH₂—, —CH═CH—CH═CH—, ethynyl, ethynyl-containing hydrocarbongroups, 1,3-cyclopentenediyl, 1,4-cyclohexenediyl, as well as aromaticlinking groups, such as 1,2-, 1,3-, and 1,4-phenylene, 4,4′-biphenylene,naphthalen-1,5-diyl, and bisphenol A ether groups. Any two, three, ormore linking groups identified above can be linked together as well,such as two methylene groups on a phenylene group, i.e., —CH₂-C₆H₄-CH₂—.

The foregoing exemplified linking groups for R are suitable for linkingtwo epoxide groups. However, a generic set of trifunctional,tetrafunctional, and higher functional epoxy resins are also consideredherein wherein one, two, or a higher number of hydrogen atoms from anyof the exemplified linking groups provided above for R are replaced byone, two, or a higher number of epoxide groups, respectively (e.g.,1,3,5-triglycidylbenzene).

In some embodiments, the hydrocarbon group R contains only carbon andhydrogen atoms. In other embodiments, the hydrocarbon group R alsoincludes one, two, three, or more heteroatoms or heteroatom groups. Theheteroatoms are typically one or more selected from oxygen (O), nitrogen(N), sulfur (S), or a halogen, such as, for example, fluorine, chlorine,bromine, and iodine atoms. Heteroatoms can be included as, for example,ether (—O—), amino (—NH—, —N═, or as a tertiary amine group), orthioether. Some heteroatom groups include hydroxy (OH), carbonyl(—C(═O)—), organoester (—C(═O)O—), amide (—C(═O)NH—), urea, carbamate,and the like. The heteroatom or heteroatom-containing group can eitherinsert between two carbon atoms engaged in a bond, or between carbon andhydrogen atoms engaged in a bond, or replace a carbon or hydrogen atom.A particular example of a linking group R containing two oxygen atoms isbisphenol A and its derivatives, which are typically functionalized withglycidyl groups via ether bonds.

In particular embodiments, the epoxy resin is a glycidyl derivative,which can be conveniently expressed as a sub-generic formula of Formula(1) above by the following structural formula:

The glycidyl derivative can be any of those compounds containingglycidyl groups, typically produced by reacting epichlorohydrin with apolyhydric molecule, such as a dihydric, trihydric, or tetrahydricmolecule. The polyhydric molecule can be, for example, a polyhydricalcohol, i.e., polyol (e.g., diol, triol, or tetrol, or genericallydefined as R—(OH)_(n) where n is as above except that it is a minimum of2), polyamine (e.g., diamine, triamine, or tetramine), or polycarboxylicacid (e.g., malonic, succinic, glutaric, adipic, or terephthalic acids).

Some particular examples of difunctional epoxy resins include diglycidylethers of a diol (i.e., glycol), wherein some examples of diols includeethylene glycol, diethylene glycol, triethylene glycol, propyleneglycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol,1,6-hexanediol, tetraethylene glycol, pentaethylene glycol, bisphenol A,bisphenol AF, bisphenol F, bisphenol S, neopentyl glycol,2,2,4,4-tetramethyl-1,3-cyclobutanediol, catechol, resorcinol,dihydroxyquinone, thiodiglycol, and 4,4′-dihydroxybiphenyl. Some epoxyprepolymer resins are of the following general formula, wherein m can be0, 1, 2, 3, 4, 5, 10, or a number up to, for example, 20, 25, 30, 40, or50 or a number within a range bounded by any two of these values:

Some particular examples of trifunctional and tetrafunctional epoxyresins include triglycidyl and tetraglycidyl ethers of a triol ortetrol, respectively, wherein some examples of triols include glycerol,1,3,5-trihydroxybenzene (phloroglucinol), trimethylolethane,trimethylolpropane, triethanolamine, and 1,3,5-triazine-2,4,6-triol(cyanuric acid). An example of a tetrol is pentaerythritol.

The difunctional, trifunctional, tetrafunctional, or higher functionalepoxy resin can also be, for example, a diglycidyl, triglycidyl,tetraglycidyl, or higher polyglycidyl ether of a phenol novolak resin orbisphenol A novolak resin. Such resins are well known in the art, asdescribed, for example, in U.S. Pat. No. 6,013,730, which is hereinincorporated by reference in its entirety.

In some embodiments, one of the di-, tri-, tetra-, or higherglycidylated materials described above is used as a primer to coat (andbond with) the carbon fiber, and a second (i.e., overlayer) of di-,tri-, tetra-, or higher glycidylated material is coated onto the primer.Typically, a thermal treatment is applied after applying the primer coatand before applying the overlayer. For example, in some embodiments,ethylene glycol diglycidyl ether is applied as a primer onto the carbonfiber surface, a thermal treatment is applied, followed by an overlayerof a different glycidylated material, such as bisphenol A diglycidylether. In a more particular embodiment, the carbon fiber surface isgrafted with epoxide groups, such as by treatment with a solution (e.g.,0.5%, 1%, or 2% by weight) of ethylene glycol diglycidyl ether in wateror aqueous solution, while undergoing (or followed) by thermal treatmentof the wet carbon fibers at an elevated temperature of, for example, 80°C., 90° C., 100° C., 110° C., 120° C., 130° C., 140° C., 150° C., 160°C., 170° C., or 180° C., or a temperature within a range bounded by anytwo of the foregoing values, before coating with an overlayer of adifferent glycidylated material. The advantage of the foregoing primerprocess is that it provides a denser covalent grafting of epoxide groupsat the surface of the fiber, which increases the number of covalentbinding sites between the epoxy sizing and carbon fiber surface.

The epoxy-containing sizing agent, described above, is completely orpartially crosslinked (i.e., completely or partially cured) withcrosslinking molecules (curing agents) possessing at least two, three,four, or more epoxy-reactive groups and at least one free functionalgroup reactive with functional groups of a polymer matrix in which thecarbon fiber is to be (i.e., subsequently) incorporated. In the case ofcomplete cros slinking (i.e., complete curing), the crosslinked sizingagent possesses no free epoxy groups that could be used for furtherreaction. In the case of partial cros slinking (i.e., partial curing),the crosslinked sizing agent possesses free (i.e., remaining) epoxygroups that could be used for further reaction, such as covalent bindingwith a precursor polymer matrix into which it is incorporated, orreaction with a bifunctional or multifunctional linking group thatfacilitates binding with a polymer matrix. The term “crosslinked”, asused herein, means that at least two epoxy groups (or perhaps three,four, or more) of the sizing agent are covalently interconnected by acrosslinking molecule via covalent bonds established between the atleast two epoxy groups and an equivalent number of epoxy-reactive groupsof the cros slinking molecule.

The epoxy-reactive groups in the crosslinking molecule can be anyepoxy-reactive group known in the art, such as an isocyanate, hydroxy(e.g., alcohol or phenol), amino (—NH₂ or —NHR, where R is a hydrocarbongroup), carboxylic acid (—C(O)OH), thiol (—SH), amide (—C(O)NH₂ or—C(O)NHR) group, or anhydride, or a combination thereof. The at leastone free functional group in the crosslinking molecule can be any group,known in the art, that can be reactive with functional groups of apolymer matrix. The at least one free functional group can be,independently, for example, any of the exemplary groups provided abovefor epoxy-reactive groups, if these groups are reactive with functionalgroups of the polymer precursor in which the carbon fibers are to beincorporated. For example, if a polymer precursor in which the carbonfibers are being incorporated possesses available hydroxy groups, the atleast one free functional group on the crosslinking molecule may beselected as a hydroxy-reactive group, such as isocyanate, carboxylic, oraldehyde; or, as another example, if the polymer precursor in which thecarbon fibers are being incorporated possesses available unsaturatedcarbon-carbon bonds, the at least one free functional group on thecrosslinking molecule may be selected as an unsaturated group (e.g.,alkenyl or vinyl), to be subsequently crosslinked by vinyl additionpolymerization, or the free functional group may be selected as a thiolgroup, which can react with an unsaturated group of the precursormatrix. In some embodiments, the crosslinking molecules, or a portionthereof, possess at least two, three, or more free functional groups.

In some embodiments, the epoxy-reactive groups in the crosslinkingmolecule are equivalent to the at least one free functional group. Forexample, the reactive groups on the crosslinking molecule can be, forexample, all isocyanate, all hydroxy, all amino, or all carboxylicgroups. In other embodiments, the epoxy-reactive groups and at least onefree functional group in the crosslinking molecule are different. Forexample, the epoxy-reactive groups may be selected from isocyanate,hydroxy, or carboxylic acid groups, while the one or more freefunctional groups may be selected from crosslinkable unsaturated groups,such as alkenyl, cycloalkenyl, or alkynyl groups; or alternatively, theepoxy-reactive groups may be selected from hydroxy groups, while the oneor more free functional groups are selected from amino, carboxylic acid,or carboxylic acid ester groups.

In order for the crosslinking molecules to effect crosslinking betweenepoxy groups of the sizing agent, at least a portion of the crosslinkingmolecules are engaged in crosslinking bonds via at least two of theirepoxy-reactive groups, wherein the term “at least a portion” or “aportion” can refer to an amount that is above 0% and precisely, about,at least, above, up to, or less than, for example, 1%, 2%, 5%, 10%, 20%,30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 98%, 99%, or 100%. The term“about”, as used herein, generally indicates no more than ±10%, 5%, 2%,or 1% of a number, e.g., “about 50%” can mean, in its broadest sense,45-55%. The crosslinking bond can be any of the resulting bonds, knownin the art, resulting from reaction between an epoxy group andepoxy-reactive group. For example, as known in the art, a hydroxy groupand epoxy group react to form an ether linkage with pendant hydroxygroup by ring opening of the epoxy group; an amino group and epoxy groupreact to form an amino linkage with pendant hydroxy group by ringopening of the epoxy group; a carboxylic acid group and epoxy groupreact to form an ester linkage with pendant hydroxy group by ringopening of the epoxy group; and an isocyanate group and epoxy groupreact to form an oxazolidone ring linkage.

In a first set of embodiments, at least a portion of the crosslinkingmolecules possess at least two (e.g., two, three, four, or more)epoxy-reactive groups and at least one non-epoxy-reactive group (e.g.,unsaturated group) that functions as a free functional group forsubsequent reaction with a precursor polymer matrix, and at least aportion of these cros slinking molecules are engaged via all of theirepoxy-reactive groups in an equivalent number of crosslinking bonds withepoxy groups of the sizing agent. Thus, in the latter embodiment, aftercrosslinking with the epoxy sizing agent, the crosslinking moleculesbear at least one free functional group that is not an epoxy-reactivegroup. The foregoing embodiment is generically depicted in FIG. lA forthe specific case of a diisocyanate crosslinking molecule, wherein thesolid circle on the diisocyanate represents the free functional groupuseful in subsequent crosslinking with a polymer matrix. Although FIG.1A depicts diisocyanate crosslinking molecules, the isocyanate groupsmay be replaced with other epoxy-reactive groups (e.g., hydroxy,carboxylic acid, or amino groups). Moreover, the number of isocyanateand/or other epoxy-reactive groups is not limited to two, but may be,for example, three, four, or more, with all epoxy-reactive groupscrosslinked with an equivalent number of epoxy groups of the sizingagent for at least a portion of the cros slinking molecules. Likewise,the number of free functional groups may or may not be greater than 1,e.g., 2, 3, or more.

In a second set of embodiments, at least a portion of the crosslinkingmolecules possess only epoxy-reactive groups. Since at least two of theepoxy-reactive groups of each crosslinking molecule are required toengage in crosslinking bonds with an equivalent number of epoxy groupsof the sizing agent, each crosslinking molecule bears at least three(e.g., three, four, five, or more) epoxy-reactive groups in order topermit at least one free epoxy-reactive group to remain aftercrosslinking with the sizing agent. The free epoxy-reactive group servesas a free functional group useful in subsequent crosslinking with aprecursor polymer matrix. Thus, in the latter embodiment, aftercrosslinking with the epoxy sizing agent, the crosslinking moleculesbear at least one free functional group that is an epoxy-reactive group.For example, if the crosslinking molecule is a triisocyanate, at least aportion or all of the triisocyanate molecules, after crosslinking,should bear at least one free isocyanate group for subsequent reactionwith a precursor polymer matrix having isocyanate-reactive groups. Theforegoing embodiment is also generically depicted in FIG. 1B when thefree functional group, represented by the solid circle on thediisocyanate crosslinking molecule, is taken as one or more otherisocyanate groups, which corresponds to the crosslinking molecule beinga triisocyanate, tetraisocyanate, or higher functional polyisocyanate.As shown, the free isocyanate group may react with a vinyl group, ifpresent, of the precursor polymer matrix by mechanisms known in the art(e.g., J.-L. Pang, et al., International Journal of Quantum Chemistry,Vol. 109, 801-810, 2009) and/or with other isocyanate-reactive groups ofthe precursor polymer matrix (e.g., hydroxy, amine, thiol, amide, orepoxy).

In a third set of embodiments, at least a portion of the crosslinkingmolecules possess at least two (e.g., two, three, four, or more)epoxy-reactive groups and at least one non-epoxy-reactive group (e.g.,unsaturated group) that functions as a free functional group forsubsequent reaction with a precursor polymer matrix, and at least aportion of these crosslinking molecules are engaged via less than all oftheir epoxy-reactive groups in an equivalent number of crosslinkingbonds with epoxy groups of the sizing agent. Thus, in the latterembodiment, after crosslinking with the epoxy sizing agent, since lessthan all of the epoxy-reactive groups of the crosslinking molecules areengaged in crosslinking bonds, the crosslinking molecules, ascrosslinked, possess at least one free epoxy-reactive group in additionto the at least one free functional group that is not an epoxy-reactivegroup. The at least one free epoxy-reactive group on the crosslinkingmolecules can advantageously also engage in covalent bonding with apolymer matrix in the event the polymer matrix possesses groups reactivewith the epoxy-reactive group (e.g., hydroxyl, carboxylic acid, epoxy,or anhydride groups). The foregoing embodiment is generically depictedin FIG. 2 for the specific case of a diisocyanate crosslinking molecule,wherein the solid circle on the diisocyanate represents a freefunctional (non-epoxy-reactive) group useful in subsequent crosslinkingwith a polymer matrix. As shown, at least a portion of the crosslinkingmolecules in FIG. 2, as crosslinked, also bear at least one freeepoxy-reactive group in addition to the at least one free functionalgroup that is not an epoxy-reactive group. Although FIG. 2 depictsdiisocyanate crosslinking molecules, the isocyanate groups may bereplaced with other epoxy-reactive groups (e.g., hydroxy, carboxylicacid, or amino groups). Moreover, the number of isocyanate and/or otherepoxy-reactive groups is not limited to two, but may be, for example,three, four, or more, at least one of which remains free in addition tothe free functional group that is a non-epoxy-reactive group. In theevent that the crosslinking molecules possess two epoxy-reactive groupsin addition to a free functional group that is not an epoxy-reactivegroup, a portion of the cros slinking molecules may be engaged in onlyone cros slinking bond with epoxy groups of the sizing agent, but, asspecified above, at least a portion of the cros slinking moleculesshould be engaged via at least two crosslinking bonds with epoxy groupsof the sizing agent in order to permit at least some crosslinkingbetween epoxy groups.

In one embodiment, the crosslinking molecules, before engaging incrosslinking with the sizing agent, possess at least three isocyanategroups. After crosslinking, at least a portion of the crosslinkingmolecules are engaged in at least two crosslinking bonds with anequivalent number of epoxy groups of the sizing agent, and, at the sametime, at least a portion of the crosslinking molecules possess a freeisocyanate group that functions as a free functional group forsubsequent reaction with a precursor polymer matrix. Thus, according tothe instant disclosure, all of the crosslinking molecules cannot beengaged in crosslinking bonds using all of the isocyanate groups, sincethis would not leave a free functional group; while, at the same time,all of the crosslinking molecules cannot be engaged in only onecrosslinking bond using only one isocyanate group (which would leave atleast two free functional groups) because then no crosslinking wouldoccur between epoxy groups. In other embodiments, the foregoingisocyanate groups are replaced with other epoxy-reactive groups, such asselected from hydroxy, carboxylic acid, amino, thiol, and/or amidegroups.

In a second embodiment, the crosslinking molecules, before engaging incrosslinking with the sizing agent, possess at least two isocyanategroups and at least one crosslinkable unsaturated group (serving as freefunctional group). After crosslinking, at least a portion of thecrosslinking molecules are engaged in at least two crosslinking bondswith an equivalent number of epoxy groups of the sizing agent. If aportion of the crosslinking molecules are engaged, via less than the atleast two isocyanate groups, in crosslinking bonds between epoxy groups,then this portion of crosslinked molecules will possess at least onefree isocyanate group in addition to the crosslinkable unsaturatedgroup. In other embodiments, the foregoing isocyanate groups arereplaced with other epoxy-reactive groups, such as selected fromhydroxy, carboxylic acid, and amino groups. Morevoer, in embodimentswhere the epoxy-reactive groups are selected from hydroxy, carboxylicacid, amino, thiol, and/or amide groups, the unsaturated group may alsobe replaced with one or more of the aforesaid groups.

Some examples of crosslinking molecules containing three isocyanategroups include toluene-2,4,6-triyl-triisocyanate (CAS 7373-26-4),2,4,6-trimethyl-benzene-1,3,5-triyl triisocyanate (CAS 65373-49-1),tris(6-isocyanatohexyl) isocyanurate (CAS 3779-63-3), triisocyanatetriphenylthiophosphate (CAS 4151-51-3), methylidynetri-p-phenylenetriisocyanate (triphenylmethane 4,4′,4″-triisocyanate, CAS 2422-91-5),1,3,5-triazine-2,4,6-triisocyanate, and(2,4,6-trioxotriazine-1,3,5(2H,4H,6H)-triyl)tris(hexamethylene) (CAS3779-63-3), as well as the numerous aliphatic triisocyanates known inthe art (e.g., 4-isocyanate methyl-1,8-octamethylene diisocyanate), asdescribed in U.S. Pat. No. 4,314,048, and the numerousN,N′,N″-tris(6-isocyanatohexyl)-isocyanurates known in the art, asdescribed in U.S. Pat. No. 4,801,663, the contents of which are hereinincorporated by reference in their entirety. Some examples ofcrosslinking molecules containing four isocyanate groups includetetraisocyanatosilane (CAS 3410-77-3),4,4′-benzylidenebis(6-methyl-m-phenylene) tetraisocyanate (CAS28886-07-9),(benzene,1,1′-(phenylmethylene)bis[2,4-diisocyanato-5-methyl-) (CAS28886-07-9), and the numerous triphenylmethane tetraisocyanatederivatives known in the art, as described in U.S. Pat. Nos. 3,707,486and 3,763,110, the numerous methylene-bridged aromatic tetraisocyanatecompositions described in U.S. Pat. No. 3,904,666, as well as thosedescribed in U.S. Pat. No. 3,763,110, the contents of which are hereinincorporated by reference in their entirety. Some examples ofcrosslinking molecules containing more than four isocyanate groups arethe polyisocyanates, as known in the art, such as polymethylenepolyphenyl polyisocyanate (CAS 9016-87-9) and those described in U.S.Pat. No. 4,801,663, the contents of which are herein incorporated byreference in their entirety. According to the instant disclosure, afterthe isocyanate-containing crosslinking molecule, described above, hasbeen crosslinked with the epoxy sizing agent, at least a portion of thecrosslinking molecules possess at least one free (available) isocyanategroup that can be used for subsequent crosslinking to a precursorpolymer matrix containing isocyanate-reactive groups (e.g., hydroxy,carboxylic acid, amino, thiol, and/or amide groups).

Some examples of crosslinking molecules containing at least twoisocyanate groups and at least one unsaturated group include4-cyclohexene-1,2-dicarbonyl diisocyanate (CAS 63712-56-1),cyclohexene-1,4-diisocyanate, 4,4′-dicyclohexene methane diisocyanate,cyclopentene-1,3-diisocyanate, and those under the trade name Desmolux®.Several of these types of unsaturated polyisocyanates are described in,for example, U.S. Application Pub. No. 2013/0196162, the contents ofwhich are herein incorporated by reference. Methods for producing suchalkenyl isocyanates are also well known in the art, as evidenced by U.S.Pat. Nos. 2,958,704 and 3,898,258, the contents of which are hereinincorporated by reference in their entirety. In some embodiments, theunsaturated group is preferably in a terminal position in order for theunsaturated group to be more available for subsequent reaction.According to the instant disclosure, after the unsaturatedisocyanate-containing crosslinking molecule, described above, has beencrosslinked with the epoxy sizing agent, the crosslinking moleculespossess at least one free (available) unsaturated group that can be usedfor subsequent crosslinking to a precursor polymer matrix containinggroups reactive with the free unsaturated group, and may or may not alsocontain one or more free isocyanate groups, as long as at least aportion of the crosslinking molecules are crosslinked via at least twoof their isocyanate groups.

Some examples of crosslinking molecules containing three hydroxy groupsinclude glycerol (as well as the ethylene oxide or propylene oxidetriols based on glycerol), trimethylol methane, phloroglucinol, cyanuricacid, 1,3,5-pentanetriol, 3-methyl-1,3,5-pentanetriol,1,4,7-heptanetriol, 1,2,7-heptanetriol, and 1,2,4-cyclohexanetriol. Someexamples of crosslinking molecules containing at least four hydroxygroups include pentaerythritol, 4-(3-hydroxypropyl)-1,4,7-heptanetriol,7-(4-hydroxyphenyl)-1,2,7-heptanetriol, 2,2,4,4,-pentanetetrol,1,1,1,5,5,5-hexafluoro-2,2,4,4-pentanetetrol,2,4-dimethyl-1,2,4,5-pentanetetrol, 1,1,5,5-pentanetetrol,1,1,7,7-heptanetetrol, 1,3,5,6-heptanetetrol, the tetrahydroxylatedbenzenes (e.g., 1,2,4,5-tetrahydroxybenzene),3-(2-hydroxyethyl)-4-methyl-1,2,3,4-pentanetetrol, thehydroxyl-terminated polybutadienes, and polyester polyols (e.g.,polycaprolactone tetrols). The crosslinking molecule may also containmore than four hydroxy groups, as in 1,2,3,4,5-pentahydroxypentane(xylitol). Any of the foregoing exemplary cros slinking molecules mayalso have one or more hydroxy groups replaced with, for example, one ormore amino, carboxylic acid, thiol, or amide groups. Some examples ofsuch bifunctional crosslinking molecules include3-amino-1,5-pentanediol, 3-amino-3-(2-hydroxyethyl)-1,5-pentanediol,3,5-dihydroxyaniline (3,5-dihydroxyphenylamine, CAS 20734-67-2),(3R,4R)-4-amino-5-methylene-1,3,7-heptanetriol,3,4-dihydroxy-benzeneacetic acid (CAS 102-32-9), 2,2-dihydroxyaceticacid, 3-(2,4-dihydroxyphenyl)propionic acid (CAS 5631-68-5), and thetrihydroxybenzoic acids (e.g., gallic acid). According to the instantdisclosure, after the hydroxy-containing crosslinking molecule,described above, has been crosslinked with the epoxy sizing agent, atleast a portion of the crosslinking molecules possess at least one free(available) hydroxy, amino, carboxylic acid, thiol, or amide group thatcan be used for subsequent crosslinking to a precursor polymer matrixcontaining suitably reactive groups.

Some examples of crosslinking molecules containing at least two hydroxygroups and at least one unsaturated group include 2-butene-1,4-diol,2-butyn-1,4-diol, 3-butene-1,2-diol, 4-pentene-1,2-diol,4-pentene-1,3-diol, 2-methyl-2-pentene-1,4-diol,3-fluoro-4-pentene-1,2-diol, 2,4-dimethyl-4-pentene-1,3-diol,4-pentene-1,2,3-triol, 5-hexene-1,2-diol, 5-hexene-1,3-diol,5-hexene-1,2,3-triol, 6-heptene-1,2-diol, 2-methyl-6-heptene-1,2-diol,6-heptene-1,2,3-triol, 1,4-cyclohexenediol, and1,2-dihydroxycyclohexene. In some embodiments, the unsaturated group ispreferably in a terminal position (e.g., in 3-butene-1,2-diol or4-pentene-1,2-diol) in order for the unsaturated group to be moreavailable for subsequent reaction. According to the instant disclosure,after the unsaturated hydroxy-containing crosslinking molecule,described above, has been crosslinked with the epoxy sizing agent, thecrosslinking molecules possess at least one free (available) unsaturatedgroup that can be used for subsequent crosslinking to a precursorpolymer matrix containing groups reactive with the free unsaturatedgroup, and may or may not also contain one or more free hydroxy groups,as long as at least a portion of the crosslinking molecules arecrosslinked via at least two of their hydroxy groups.

Some examples of crosslinking molecules containing three amino groupsinclude diethylenetriamine (DETA), cyclohexane-1,3,5-triamine, thepolyether triamines (e.g., polyoxypropylene triamines), melamine,spermidine, bis(hexamethylene)triamine, 1,2,4-benzenetriamine, andguanidine. Some examples of crosslinking molecules containing four aminogroups include triethylenetetramine (TETA), spermine,1,2,4,5-benzenetetramine, pentane-1,1,1,5-tetraamine, andpentane-1,2,4,5-tetramine. The crosslinking molecule may also containmore than four amino groups, as in the polyamino molecules well known inthe art, as evidenced in U.S. Pat. No. 4,709,003, the contents of whichare herein incorporated by reference in their entirety. Theamino-containing crosslinking molecule may also be an N-alkyl (e.g.,N-methyl or N-ethyl) analog, provided that at least two amino groupsselected from primary and secondary amines are present in theamino-containing crosslinking molecule before crosslinking. According tothe instant disclosure, after the amino-containing crosslinkingmolecule, described above, has been crosslinked with the epoxy sizingagent, at least a portion of the crosslinking molecules possess at leastone free (available) amino group that can be used for subsequentcrosslinking to a precursor polymer matrix containing amino-reactivegroups (e.g., epoxy, carboxylic acid, carboxylic acid ester, anhydride,or aldehyde groups).

Some examples of crosslinking molecules containing at least two aminogroups and at least one unsaturated group include 1,4-diamino-2-butene,N-propyl-1,4-diamino-2-butene, 2-pentene-1,4-diamine,2-pentene-1,5-diamine, 2-pentene-2-chloro-1,5-diamine,5-fluoro-2-pentene-1,4-diamine, 5,5-difluoro-2-pentene-1,4-diamine,4-hexene-1,2-diamine, 2-methyl-1-hexene-1,4-diamine,2-hexene-1,6-diamine, 3-chloro-3-hexene-1,6-diamine, and5-hexene-1,2-diamine. In some embodiments, the unsaturated group ispreferably in a terminal position (e.g., in 5-hexene-1,2-diamine) inorder for the unsaturated group to be more available for subsequentreaction. According to the instant disclosure, after the unsaturatedamino-containing crosslinking molecule, described above, has beencrosslinked with the epoxy sizing agent, the crosslinking moleculespossess at least one free (available) unsaturated group that can be usedfor subsequent crosslinking to a precursor polymer matrix containinggroups reactive with the free unsaturated group, and may or may not alsocontain one or more free amino groups, as long as at least a portion ofthe cros slinking molecules are crosslinked via at least two of theiramino groups.

Some examples of crosslinking molecules containing three carboxylic acidgroups include citric acid, isocitric acid,1,2,4-cyclohexanetricarboxylic acid, propane-1,2,3-tricarboxylic acid,benzene-1,3,5-tricarboxylic acid (trimesic acid),benzene-1,2,4-tricarboxylic acid (trimellitic acid), andbenzene-1,2,3-tricarboxylic acid. Some examples of crosslinkingmolecules containing four carboxylic acid groups include1,2,4,5-benzenetetracarboxylic acid, biphenyl-3,3′,5,5′-tetracarboxylicacid (CAS 4371-28-2), (18-crown-6)-2,3,11,12-tetracarboxylic acid (CAS61696-54-6), tetrahydrofuran-2,3,4,5-tetracarboxylic acid (CAS26106-63-8), and 1,2,3,4-butanetetracarboxylic acid (CAS 1703-58-8).Some examples of crosslinking molecules containing more than fourcarboxylic acid groups include benzene-1,2,3,4,5-pentacarboxylic acid,benzenehexacarboxylic acid (mellitic acid),1,2,3,4,5,6-cyclohexanehexacarboxylic acid, and2-aminobenzo[b]thiophene-3,4,5,6,7-pentacarboxylic acid 3-ethyl4,5,6,7-tetramethyl ester (CAS 66385-68-0). According to the instantdisclosure, after the carboxy-containing crosslinking molecule,described above, has been crosslinked with the epoxy sizing agent, atleast a portion of the crosslinking molecules possess at least one free(available) carboxylic acid group that can be used for subsequentcrosslinking to a precursor polymer matrix containing suitably reactivegroups (e.g., amino, epoxy, or isocyanate groups).

Some examples of crosslinking molecules containing at least twocarboxylic acid groups and at least one unsaturated group includeaconitic acid, maleic acid, fumaric acid (2-butenedioic acid),2-vinylmalonic acid, 2-allylmalonic acid (CAS 2583-25-7),2-butenylmalonic acid, 2-allyl-2-(1-butenyl)malonic acid,2-allyl-2-ethylmalonic acid, 2,2-di(3-butenyl)malonic acid,2-(2-pentenyl)malonic acid, 2-(4-pentenyl)malonic acid,2-methyl-2-(4-pentenyl)malonic acid, 2-allylsuccinic acid,2-(3-butenyl)succinic acid, 2-(2-butenyl)succinic acid, 2-allylglutaricacid, 3-allylglutaric acid, 2-allyladipic acid, 3-allyladipic acid,4-allyladipic acid, 2-pentenedioic acid, 2-octenedioic acid, some ofwhich are disclosed in U.S. Pat. Nos. 4,326,987 and 4,508,637, thecontents of which are herein incorporated by reference in theirentirety. In some embodiments, the unsaturated group is preferably in aterminal position (e.g., in 2-(4-pentenyl)malonic acid) in order for theunsaturated group to be more available for subsequent reaction.According to the instant disclosure, after the unsaturatedcarboxy-containing crosslinking molecule, described above, has beencrosslinked with the epoxy sizing agent, at least a portion of thecrosslinking molecules possess at least one free (available) unsaturatedgroup that can be used for subsequent crosslinking to a precursorpolymer matrix containing groups reactive with the free unsaturatedgroup, and may or may not also contain one or more free carboxy groups,as long as at least a portion of the crosslinking molecules arecrosslinked via at least two of their carboxy groups. The reactionbetween epoxides and carboxylic acids or between epoxides and anhydridesis typically catalyzed by catalysts that may be amine-based,ammonium-based, phosphonium-based, or metal-based, as further describedin W. J. Blank, et al., “Catalysis of the Epoxy-Carboxyl Reaction”,International Waterborne High-Solids and Powder Coatings Symposium, Feb.21-23, 2001, New Orleans, La., USA, the contents of which are hereinincorporated by reference in their entirety.

In some embodiments, the crosslinking molecule, described above, is thesole crosslinking (i.e., curing) agent. In other embodiments, thecrosslinking molecule, described above, may be used in combination withone or more additional curing (crosslinking) agents that have only twoepoxy-reactive groups without a third group that could function as afree functional group or crosslinking group. The additional curing agentcan be, for example, a diamine, such as ethylene diamine (EDA),1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane,1,5-diaminopentane, o-, m-, or p-phenylenediamine, methylenedianiline,3,3′- and 4,4′-diaminodiphenylsulfones, triethylene glycol diamine,tetraethylene glycol diamine (available as polyetheramine JEFFAMINE® D,ED and EDR series of compositions), piperazine, imidazole,2-methylimidazole, isophoronediamine, m-xylenediamine, as well as theirN-alkyl (e.g., N-methyl or N-ethyl) analogs, provided that two aminogroups selected from primary and secondary amines are present in theadditional curing agent before crosslinking. In other embodiments, theadditional curing agent may be a dicarboxylic acid (e.g., oxalic acid,malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid,suberic acid, or terephthalic acid), a diol (e.g., ethylene glycol,propylene glycol, diethylene glycol, or triethylene glycol), or adiisocyanate (e.g., toluene 2,4-diisocyanate, 1,4-phenylenediisocyanate, methylene diphenyl diisocyanate, isophorone diisocyanate,or 3,3′-dimethyl-4,4′-biphenylene diisocyanate). In some embodiments,any one or more of the above-disclosed classes or specific types ofadditional curing agents are excluded.

In some embodiments, at least a portion of epoxide groups in the sizingagent are available as uncrosslinked epoxide groups, which correspondsto a fraction conversion (curing degree) of epoxide groups thatmaintains the sizing agent in flexible form, such as a gel. To maintainthe sizing agent in flexible or semi-rigid form, the curing degree ofepoxide groups is preferably no more than (or less than) about 0.4,0.45, 0.5, 0.55, 0.6, 0.65, or 0.7. A curing degree above 0.6, or at orabove 0.65 or 0.7, generally results in a sizing agent that issubstantially rigid. As used herein, and as generally recognized in theart, the terms “curing degree of epoxide groups” refers to the number ofepoxide groups that have undergone ring-opening crosslinking relative tothe number of epoxide groups that were originally uncrosslinked beforethe cure of the epoxy. In different embodiments, the curing degree ofepoxide groups is about, up to, less than, at least, or above, forexample, 0.95, 0.9, 0.85, 0.8, 0.75, 0.7, 0.65, 0.6, 0.55, 0.5, 0.45,0.4, 0.35, 0.3, 0.25, 0.2, 0.15, or 0.1, or a curing degree within arange bounded by any two of the foregoing values, or between any of theforegoing values and 1 (wherein a curing degree of 1 corresponds to 100%crosslinking with no uncrosslinked epoxy groups). As used herein, theterm “about” generally indicates within±0.5%, 1%, 2%, 5%, or up to±10%of the indicated value.

In particular embodiments, about 2 parts of a diisocyanate moleculebearing an aliphatic urethane acrylate moiety (e.g., Desmolux® D 100)and about 1 part of a tetrafunctional epoxy resin sizing agent (e.g.,MY721, also known as Araldite®MY721) are reacted so that the ratio ofthe concentrations of isocyanate groups to epoxide groups in the mix is,for example, precisely or about 0.7, 0.75, 0.8, 0.85, 0.9, or 0.95, or aratio within a range therein (e.g., 0.75-0.9, or 0.8-0.9, or 0.75-0.85,or 0.8-0.85, or 0.82-0.88, or 0.82-0.86).

In another aspect, the invention is directed to a solid composite inwhich the surface-functionalized carbon fibers, described above, areembedded (i.e., incorporated) within a polymeric matrix. The polymer ofthe matrix can be any polymer suitable for use in a high strengthapplication, and may be a thermoplastic or thermoset.

Some particular matrix polymers considered herein are those resultingfrom vinyl-addition polymerization of an unsaturated precursor resin orunsaturated monomers. By being unsaturated, the precursor resin ormonomer contains carbon-carbon double bonds. The polymeric matrix can bederived from, for example, curing any of the acrylate or methacrylatemonomers known in the art (e.g., acrylic acid, methacrylic acid,methylmethacrylate, hydroxyethylmethacrylate), acrylonitrile, ethylene,propylene, styrene, divinylbenzene, 1,3-butadiene, cyclopentene, vinylacetate, vinyl chloride, or a cycloolefin (e.g., cyclohexene,cycloheptene, cyclooctene, or norbornene), or a fluorinated unsaturatedmonomer, such as vinylidene fluoride, fluoroethylene, ortetrafluoroethylene, or a bromated unsaturated monomer (e.g.,DGEBA-based vinyl ester monomer with bromo substitution on the aromaticring). The polymer matrix can be a homopolymer, or alternatively, acopolymer, e.g., block, random, alternating, or graft copolymer of twoor more different types of monomers, such as any of those mentionedabove.

The matrix polymer can also be any of the condensation polymers known inthe art. The condensation polymer can be, for example, a polyester,polyamide, polyurethane, or phenol-formaldehyde, or a copolymer thereof,or a copolymer with any of the addition polymers described above. Inparticular embodiments, the matrix polymer is a thermoplastic selectedfrom polyether ether ketone (PEEK), polycarbonates, polymethacrylicacids, polyesters, polylactic acids, polyglycolic acids, thermoplasticpolyurethanes, polymethacrylates, polymethylmethacrylates, Nylon 6,Nylon 6,6, polysulfones, polyvinylalcohols and polyimides.

In a first particular embodiment, the matrix polymer is derived from avinyl ester resin by curing methods well-known in the art. Vinyl esterresins are known to possess terminal carbon-carbon double bonds. Asknown in the art, a vinyl ester resin is generally formed by reactionbetween a diepoxide, triepoxide, or higher polyepoxide (e.g., asdescribed above under Formulas 1, 1a, and 2) and an unsaturatedmonocarboxylic acid, such as acrylic or methacrylic acid. The generalprocess for producing an exemplary difunctional divinyl ester isprovided as follows:

In the above scheme, Formula (3) depicts an exemplary set ofdifunctional divinyl esters in which R is as defined above and R′ iseither a bond or a hydrocarbon linker R, as defined above. In particularembodiments, the diepoxy molecule depicted in the above scheme isdiglycidyl ether of bisphenol A (DGEBA). The resulting difunctionaldivinyl ester possesses two distinct reactive functional groups, i.e.,vinyl groups and hydroxy groups, either or both of which may be involvedin a reaction with the crosslinked sizing agent to form covalent bondstherewith, for covalent incorporation of the carbon fibers. In a firstembodiment, the vinyl groups of the difunctional divinyl ester crosslinkwith vinyl-reactive groups found in free functional groups of thecrosslinked sizing agent, e.g., available vinyl groups on thecrosslinked sizing agent can undergo vinyl addition crosslinking withvinyl groups in the difunctional divinyl ester (in the latterembodiment, the hydroxy groups of the difunctional divinyl ester may ormay not also form covalent bonds with the crosslinked sizing agentdepending on whether the crosslinked sizing agent also possesseshydroxy-reactive functional groups). In a second embodiment, the hydroxygroups of the difunctional divinyl ester crosslink with hydroxy-reactivegroups found in free functional or epoxy-reactive groups of thecrosslinked sizing agent, e.g., available isocyanate, carboxylic acid,carboxylic acid ester, or anhydride groups on the crosslinked sizingagent can react and form covalent bonds with hydroxy groups in thedifunctional divinyl ester (in the latter embodiment, the vinyl groupsof the difunctional divinyl ester may or may not also form covalentbonds with the crosslinked sizing agent depending on whether thecrosslinked sizing agent also possesses functional groups reactive withunsaturated groups). In a third embodiment, both the hydroxy groups andvinyl groups of the difunctional divinyl ester react and form covalentbonds with the crosslinked sizing agent, e.g., vinyl groups of thedifunctional divinyl ester crosslink with vinyl-reactive groups found infree functional groups of the crosslinked sizing agent, and hydroxygroups of the difunctional divinyl ester react and form covalent bondswith hydroxy-reactive groups found in free functional or epoxy-reactivegroups of the crosslinked sizing agent.

In a second particular embodiment, the matrix polymer is derived from anunsaturated polyester resin. Unsaturated polyester resins are known topossess internal carbon-carbon double bonds. As known in the art, anunsaturated polyester resin is generally formed by reaction between adiol, triol, tetrol, or higher polyol, such as any of the polyolsdescribed above, and an unsaturated di- or tri-carboxylic acid, such asmaleic, phthalic, isophthalic, or terephthalic acid. The general processfor producing an exemplary unsaturated polyester resin is provided asfollows:

In the above scheme, Formula (4) depicts an exemplary set of unsaturatedpolyester resins in which R is as defined above and R″ is an unsaturatedhydrocarbon linker containing a reactive alkenyl group, such as any ofthe unsaturated hydrocarbon linkers defined for R above containing thisfeature, and r is generally at least 1, 2, 3, 4, or 5, and up to 6, 7,8, 9, 10, 12, 15, 18, or 20 (or any range bounded by any two of thesevalues). The diol HO—R—OH shown in the above scheme may be replaced withor combined with a triol, tetrol, or higher functional alcohol, orgenerically defined as R—(OH)_(n) where n is as above except that it isa minimum of 2, and the dicarboxy molecule depicted in the above schemecan be replaced with or combined with a tricarboxy or higher carboxymolecule. In particular embodiments, the polyol is selected from apolyethylene glycol, such as ethylene glycol, diethylene glycol, andtriethylene glycol, and the polycarboxy is selected from maleic acid,phthalic acid, isophthalic acid, and terephthalic acid. Alkenyl groupsof the unsaturated polyester resin can react and crosslink withvinyl-reactive groups found in free functional groups of the crosslinkedsizing agent, e.g., available vinyl groups on the crosslinked sizingagent can undergo vinyl addition crosslinking with vinyl groups in theunsaturated polyester resin.

In some embodiments, covalent bonding with the polymer matrix isestablished only by the presence of crosslinking molecules according tothe invention (i.e., by the presence of free functional and/orepoxy-reactive groups), as described above. In other embodiments, one ormore bifunctional molecules containing an epoxy-reactive end and apolymer-reactive end are reacted with remaining epoxy groups of thecrosslinked sizing to further functionalize the epoxy sizing with groupsthat can covalently bond with the polymer matrix. For example, theepoxy-functionalized carbon fibers can be reacted with a bifunctionalmolecule that contains an epoxy-reactive group, for reacting with thesizing agent, as well as an unsaturated group, for reacting (typically,but by no means solely, via vinyl-addition coupling) with the matrixprecursor resin. The epoxy-reactive end of the bifunctional moleculebecomes bound to the epoxy sizing bonded with the carbon fiber, and theunsaturated portion of the difunctional molecule is free and availablefor reaction with the matrix precursor resin. In particular embodiments,the difunctional molecule is an alkenyl amine, such as allylamine(2-propen-1-amine), 3-buten-1-amine, or 4-penten-1-amine, or an alkenylalcohol, such as allyl alcohol (2-propen-1-ol), 3-buten-1-ol,4-penten-1-ol, or 4-hydroxystyrene. Alternatively, a free functionaland/or epoxy-reactive group on the crosslinked sizing agent may bereacted with a bifunctional agent to functionalize the sizing agent witha different group more suitable for reaction with the polymer matrix.For example, if the crosslinked sizing agent possesses only freeisocyanate groups, at least a portion thereof may be reacted with anunsaturated alcohol (e.g., 3-buten-1-ol) to functionalize the sizingagent with unsaturated groups in the event that the precursor polymermatrix contains unsaturated groups that can undergo vinyl addition withunsaturated groups of the sizing agent. In some embodiments, any one ormore of the above-described classes or specific types of bifunctionalmolecules are excluded.

In another embodiment, covalent bonding between the carbon fibers andthe polymeric matrix is further established by incorporating reactivegroups in the matrix precursor resin that react with the sizing agent onthe carbon fiber when the carbon fiber and the matrix precursor resinare combined. For example, a bifunctional monomer having an unsaturatedportion and an epoxy-reactive portion can be included in the matrixprecursor resin. The unsaturated bifunctional monomer can react withcomponents of the matrix precursor resin via its unsaturated end (orother portion), and also covalently bond with available epoxy groups ofthe epoxy sizing agent on the carbon fibers via its epoxy-reactive end(or other portion). The unsaturated difunctional monomer can be, forexample, an amino-containing acrylate or methacrylate, such as2-aminoethyl methacrylate, 2-(methylamino)ethylmethacrylate,2-(dimethylamino)-ethylmethacrylate, or any of the alkenyl amine oralkenyl alcohol difunctional molecules described above. The bifunctionalmolecule can alternatively be, for example, a diisocyanate, such as anyof the diisocyanates described above, wherein one of the isocyanategroups of the diisocyanate molecules remains available for reaction withhydroxy or other isocyanate-reactive groups of the polymer matrix afterattachment of the diisocyanate to the sizing agent. In some embodiments,any one or more of the above-described classes or specific types ofbifunctional molecules are excluded.

In another aspect, the invention is directed to a process for preparingthe carbon fiber described above containing an epoxy sizing agent boundto its surface. As discussed above, the original carbon fiber to bereacted with the epoxy sizing agent (i.e., precursor carbon fiber) issurface-functionalized with groups reactive with the sizing agent. Theinitial functionalization can be provided by, for example, anelectrochemical surface treatment, a plasma surface treatment, or anoxidation surface treatment based on oxidative species generated by thethermal decomposition of ozone, the details of which are well known inthe art.

The epoxy sizing can be made to covalently bond to the surface of thecarbon fiber by reacting its epoxide groups with epoxy-reactive groupslocated on the carbon fiber surface (e.g., surface hydroxyl, carboxyl,and amino groups, as described above). In other embodiments, a firstpolymer or molecule containing at least one epoxy group orepoxy-reactive group is reacted with the carbon fiber surface, and thenthe epoxy sizing is reacted with the first polymer or grafted molecule.The epoxide-reactive group can be, for example, a hydroxyl (e.g.,alcohol or phenol), carboxylic acid, thiol, amine, or amide group. Forexample, an epoxy group can be first grafted at the surface of the fiberby exposing the carbon fiber surface to a solution of ethylene glycoldiglycidyl ether (e.g., 0.5 wt %) in water and exposing the wet fiber toa temperature of about 150° C. for about 30 minutes.

The carbon fiber is contacted with the sizing agent under conditions, asknown in the art, that permit a covalent bond to be formed between theepoxy sizing agent and reactive groups located on the carbon fibersurface. In a specific embodiment, the carbon fiber is contacted with asolution or emulsion of the sizing agent, wherein the solution oremulsion of the sizing agent includes the sizing agent dispersed in asolvent carrier, e.g., water, a water-soluble solvent (e.g., acetone ormethylethylketone), or other polar or non-polar solvent, or acombination thereof or aqueous solution thereof. The sizing agent can beadmixed with solvent carrier in any desired concentration, but typicallyin an amount no more than 30% by weight of the total of sizing agent andsolvent carrier, such as 1%, 2%, 5%, 10%, 15%, 20%, or 25% by weight. Inparticular embodiments, the sizing agent is included in the carriersolution in a concentration of up to or less than 10%, and morepreferably, from 1 to 5%, 1 to 4%, 1 to 3%, or 1 to 2%. Generally, aroom temperature condition (i.e., from 15-25° C., or about 20° C.) isacceptable, but an elevated temperature may also be used to facilitatebonding. An intermediate processing step, before curing, may also beincluded, such as a rinsing, drying, or annealing step.

In some embodiments, the carbon fiber is first covalently attached to anuncrosslinked epoxy sizing agent, and the uncrosslinked sizing agentsubsequently crosslinked by reacting the sizing agent with a desiredamount of crosslinking molecules of the invention. In anotherembodiment, the carbon fiber is reacted with an epoxy sizing agent thatwas earlier at least partially crosslinked with a desired amount ofcrosslinking molecules of the invention and/or other curing agent. Insome embodiments, less than the stoichiometric amount of crosslinkingmolecules is used, in which case uncrosslinked epoxy groups remain onthe crosslinked sizing agent. In some embodiments, the amount of crosslinking molecule used provides a curing degree of no more than (or lessthan) about 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, or 0.7, which retains thesizing agent in flexible to semi-rigid form. Depending on the curingmethodology used, the curing step may be conducted at room temperatureor at an elevated temperature. The conditions used in curing are wellknown in the art. A post-processing step, after curing, may also beincluded, such as a rinsing, drying, or annealing step.

In the above-described process, the sizing agent can be advantageouslyselectively adjusted in thickness and viscosity by appropriateadjustment in conditions used in the process. For example, the sizingagent can be selectively adjusted in thickness by correspondingadjustment in the concentration of the sizing agent in the solution oremulsion of sizing agent, i.e., lower concentrations generally result inthinner layers of sizing agent and higher concentrations generallyresult in thicker layers of sizing agent. The sizing agent can beselectively adjusted in viscosity by corresponding adjustment in theamount of crosslinking molecule (with optional additional curing agent)used, i.e., lower amounts of curing agents generally result in lowerviscosities, and higher amounts of curing agents generally result inhigher viscosities. When chopped carbon fibers are desired, as preferredfor use in sheet molding, the thickness and the viscosity of the sizingagent are preferably high enough to make the tow relatively hard anddifficult to spread. When long and continuous fibers are desired, thethickness and viscosity of the sizing agent are preferably low enough tomake the tow relatively soft and easy to spread. The weight percentageof sizing agent with respect to the sum of sizing agent and carbon fiberis typically less than 1 wt. % for continuous fibers and at or abovethis amount for chopped fibers, e.g., up to 2, 5, 10, 15, 20, 25, or 30wt %.

In another aspect, the invention is directed to a process for preparinga composite that contains carbon fibers covalently embedded in a polymermatrix described above. In the method, carbon fibers coated withcompletely or partially crosslinked epoxy sizing agent are mixed withmatrix precursor resin before subjecting the mixture to a curingprocess. The matrix precursor resin can be any of the precursor resinsdescribed above, particularly an unsaturated precursor resin, such as avinyl ester resin or unsaturated polyester resin. In the curing process,epoxy-reactive and/or free functional groups on the crosslinked sizingagent react and crosslink with suitably reactive groups on the precursorresin.

Particularly in the case of unsaturated precursor matrix resin, it iscommonplace to also include an unsaturated reactive diluent as a matrixcomponent prior to curing. The unsaturated reactive diluent typicallyserves to crosslink portions of the precursor resin and facilitateinterdiffusion between the epoxy sizing and polymer matrix, which canfurther strengthen and harden the matrix in the interphase region. Inspecific embodiments, the unsaturated reactive diluent is a moleculecontaining one, two, or three vinyl groups. Some examples of unsaturatedreactive diluents include styrene, divinylbenzene, a methacrylate, anacrylate, or a vinyl ester (e.g., vinyl acetate). In some embodiments,any one or more of the above-described classes or specific types ofreactive diluents are excluded.

The conditions used in curing such precursor resins are well known inthe art, and may rely on, for example, an elevated temperature,radiative exposure (e.g., UV, microwave, or electron beam), or both, aswell as the use of an initiator, such as a peroxide (e.g., cumenehydroperoxide, butanone peroxide, t-butylperoxybenzoate, benzoylperoxide, or MEKP) or Lewis acid (e.g., BF₃), and if applicable, acatalyst, such as a metal-containing catalyst, e.g., a ROMP catalyst. Inparticular embodiments, the curing step is conducted at a temperatureselected from 125° C., 130° C., 135° C., 140° C., 145° C., 150° C., 155°C., 160° C., 165° C., 170° C., 175° C., 180° C., or 185° C., or atemperature within a range bounded by any two of these values, for acuring time selected from 0.5, 1.0, 1.5, 2.0, 2.5, or 3.0 hours, or atime within a range bounded by any two of these values, wherein it isunderstood that higher curing temperatures generally require shortercuring times to achieve the same effect. In some embodiments, a two-stepor three-step curing process is used, wherein each step employs adifferent temperature. Moreover, the cure can be conducted at roomtemperature with the help of a promoter included in the resin, such ascobalt naphthenate, cobalt octoate, or cobalt acetylacetonate, and canbe accelerated by the use of a catalyst, such as N,N-dimethylaniline andsimilar molecules.

The solid composites described herein preferably possess a significantlyincreased carbon fiber interlaminar shear strength (ILSS) relative tocomposites that include the same carbon fiber and epoxy sizing agentwith uncured sizing agent. For example, whereas a composite with uncuredsizing agent may exhibit an ILSS of about 60 MPa, the instant compositesusing partially cured epoxy sizing may exhibit an ILSS of at least 70,80, 90, or 100 MPa, or an ILSS within a range bounded by any two ofthese values.

Examples have been set forth below for the purpose of illustration andto describe certain specific embodiments of the invention. However, thescope of this invention is not to be in any way limited by the examplesset forth herein.

EXAMPLES

Overview of Experiments

Crosslinking molecules (i.e., the curing agent) having pendant reactivefunctionalities were used to form covalent bonds with a vinyl ester orunsaturated polyester matrix in order to generate stronger bondingbetween the epoxy sizing (as coated on a carbon fiber) and the polymermatrix. Moreover, if the curing agent is well chosen, it can alsogenerate additional covalent bonding between the epoxy sizing and thecarbon fiber surface. For example, isocyanate groups can form covalentbonds with hydroxy and carboxylic acid groups located at the surface ofthe carbon fiber. If the curing agent contains unsaturated groups (e.g.,an acrylate pendant group), the unsaturated group can also form covalentbonds with amine groups located at the surface of the carbon fiber viaan aza-Michael reaction. The covalent bonding formed between the epoxysizing and the polymer matrix and between the carbon fiber surface andcrosslinked sizing resulted in an improvement in the interface strengthbetween the carbon fiber and the polymer matrix. As further discussedbelow, the improved interface strength also resulted in an improvementin the mechanical properties of the corresponding composites.

In experiments described below, pendant acrylate functionalities weregrafted onto an epoxy sizing using a diisocyanate crosslinking moleculebearing an aliphatic urethane acrylate moiety (commercial productDesmolux® D 100). The isocyanate functionalities react with epoxidegroups by generating oxazolidone groups, and the acrylate functionalitycan react with a vinyl ester or unsaturated polyester matrix during itspolymerization.

Detailed Account of Experiments

Carbon fibers, surface treated and non-sized, were sized with fourdifferent types of sizings, including the sizing described in theinstant disclosure. The carbon fibers were derived frompolyacrylonitrile (PAN) precursor fibers, and possessed a tensilemodulus and tensile strength of 242 GPa and 4137 MPa, respectively. Thecarbon fibers were used in the form of a tow containing 50,000filaments. HU6-01 is a polyurethane-based thermoplastic sizing, and ATIis a reactive sizing. A partially cured epoxy sizing, with Jeffamine®T-403 as the curing agent, was also investigated for comparativepurposes.

A sizing solution was prepared as follows: 37.3 g of Desmolux® D 100curing agent was added to 15.3 g of epoxy resin Araldite®MY721 (atetrafunctional epoxy resin), and the components thoroughly mixed.Considering that the weight per epoxide is 113 in the case of MY721 andthat the weight per isocyanate is 328 in the case of Desmolux® D 100,the ratio of the concentrations of isocyanate groups to epoxide groupsused in the mix was 0.84. The mixture was allowed to stand for 30minutes at ambient temperature before being dissolved into 4 liters ofacetone. The resulting sizing solution had a concentration of 1.6 wt. %.The carbon fibers were then sized with the solution using a sizing unitmade of mirror-finished stainless steel rollers, a scraper to remove theexcess of sizing, and a multi-gallon capacity bath. After passingthrough the sizing bath, the fibers were dried in a tubular furnace at150° C. for a few minutes.

Unidirectional composites were obtained by winding the carbon fibersaround a steel frame and placing them in a two-piece steel mold. Thefibers were then impregnated with an excess of polyester resin (codename XV3175 by AOC) by layup and the excess of resin was expelled byclosing the mold with pressure. The dimensions of the composite sampleswere controlled by the dimensions of free space in the mold, which wasconstant. 1.5 wt. % of tert-butylperoxybenzoate (initiator) was earlieradded to the resin and thoroughly mixed by the use of a centrifuge(rotation speed: 3000 rpm, time: 4 minutes), with degassing of the mix,since the radical polymerization of polyester resins is very sensitiveto oxygen. The mold was then placed in a digitally controlled furnace.The volume concentration of carbon fibers, assuming that the sampleswere void free, was calculated to be around 60%. The thermal program forthe cure was 1 hour at 150° C.

The interlaminar shear strength (ILSS) and the flexural strength of thecomposites (90° and 0° ) were measured according to ASTM D2344 and ASTM790, respectively. For each carbon fiber-resin system and each test, 10specimens were tested. As known in the art, the 90° flexural strength isthe property that is the most sensitive to interfacial adhesion whenconsidering unidirectional composites (Drzal L. T., Madhukar M. “Fibermatrix adhesion and its relationship to composite mechanicalproperties”, J. Mater. Sci., 28:569-610, 1993)

Among all the sizings that were tested, the one based on the instantdisclosure resulted in the best mechanical properties (Table 1). TheILSS was increased from 67 MPa to 97 MPa (+45%) and the 90° flexuralstrength was increased from 32 MPa to 56 MPa (+75%). An improvement wasalso evident when comparing to the mechanical properties resulting froman epoxy sizing partially cured with Jeffamine® T-403.

The difference in interfacial adhesion was enough to induce asignificant improvement in the 0° flexural strength as well (Table 2),as a result of an increase in the tensile strength and the compressivestrength of the corresponding composites. Both types of epoxy sizingsshowed an increase, from 1126 MPa for the non-sized fibers to 1304 MPa(+16%) for the epoxy sizing partially cured by Jeffamine® T-403, and to1352 MPa (+20%) for the epoxy partially cured by Desmolux® D 100.

TABLE 1 ILSS and 90° flexural strength obtained with different sizingsPartially cured Partially cured epoxy sizing with epoxy sizing withisocyanate bearing No sizing HU6-01 ATI Jeffamine T-403 acrylate ILSS(Ksi) 9.7 ± 0.4 10.6 ± 0.4 11.4 ± 0.4 12.2 ± 0.4 13.7 ± 0.5 9.6 ± 0.310.4 ± 0.4 11.3 ± 0.3 11.7 ± 0.3 14.5 ± 0.4 90° flexural 4.6 ± 0.2  5.2± 0.3  5.2 ± 0.6  6.2 ± 0.9  8.1 ± 1.2 strength (Ksi) ILSS (MPa) 67 ± 3 73 ± 3 79 ± 3 84 ± 3 94 ± 4 66 ± 2  72 ± 3 78 ± 2 81 ± 2 100 ± 3  90°flexural 32 ± 1  36 ± 2 36 ± 4 43 ± 6 56 ± 8 strength (MPa)

TABLE 2 0° flexural strength obtained with different sizings Partiallycured Partially cured epoxy sizing with epoxy sizing with isocyanatebearing No sizing HU6-01 ATI Jeffamine T-403 acrylate 0° flexural 163.3± 8.1 1187 ± 11.5 200.6 ± 13.5 189.1 ± 6.3 196.1 ± 8.9 strength (Ksi) 0°flexural 1126 ± 56 1187 ± 79  1383 ± 93  1304 ± 43 1352 ± 61 strength(MPa)

In separate experiments, a carbon fiber with no sizing was compared witha carbon fiber having an epoxy sizing partially cured withisocyanate-acrylate (Desmolux D 100) crosslinker. The carbon fibers werederived from polyacrylonitrile (PAN) precursor fiber, and were used inthe form of a tow containing 12,000 filaments. The tensile modulus andtensile strength of the fibers were 248 GPa and 4510 MPa, respectively.Unidirectional composites were obtained by winding carbon fibers arounda steel frame and placing them in a two-piece steel mold. The fiberswere then impregnated with an excess of a bisphenol A epoxy acrylateresin (code name Ebecryl® 600 from Cytech) by layup and the excess ofresin was expelled by closing the mold with pressure. The resin waspreviously degassed at 90 ° C. in primary vacuum. The dimensions of thecomposite samples were controlled by the dimensions of free space in themold, which was constant. The mold containing the samples was thenexposed to an electron beam produced by a 10 MeV electron accelerator.All ionization experiments were carried out using a dynamic mode, andthe dose was adjusted by varying the translation speed of the samplecarrier. The curing of each set of samples was performed with a totaldose of 100 kGy through four passes of 25 kGy. The volume concentrationof carbon fibers, assuming that the samples were void free, wascalculated to be around 60%.

The interlaminar shear strength (ILSS) was measured according to ASTMD2344. For each carbon fiber reference, 10 specimens were tested. Thesizing based on the instant disclosure resulted in a clear improvementof the mechanical properties, as evidenced by the data in Table 3 below.In particular, the ILSS was increased from 61 MPa to 81 MPa (+33%).

TABLE 3 ILSS results for sized and non-sized fibers. Partially curedepoxy sizing with isocyanate No sizing bearing acrylate ILSS (Ksi) 8.7 ±0.5 11.7 ± 0.5 9.0 ± 0.3 11.7 ± 0.3 ILSS (MPa) 60 ± 3  81 ± 3 62 ± 2  81± 2

The instantly described approach is facile and straight-forward, and isreadily integratable in industrial operations. Moreover, the instantlydescribed process is highly cost effective by use of affordablechemicals. Considering the significant amount of carbon-fiber vinylester/polyester composites produced each year, the improved process andcompositions described herein represent a significant advance in the artof high strength composites.

While there have been shown and described what are at present consideredthe preferred embodiments of the invention, those skilled in the art maymake various changes and modifications which remain within the scope ofthe invention defined by the appended claims.

What is claimed is:
 1. A method of making a carbon fiber having on itssurface an at least partially cured sizing gent containing epoxy groups,the method comprising covalently binding on the surface of a carbonfiber a sizing agent comprised of an epoxy resin, and at least partiallycuring said sizing agent by contact thereof with a crosslinking moleculepossessing at least two epoxy-reactive groups and at least one freefunctional group reactive with functional groups of a polymer matrix inwhich the carbon fiber is to be incorporated, wherein, after said atleast partial curing step, at least a portion of said crosslinkingmolecules are engaged, via at least two of their epoxy-reactive groups,in crosslinking bonds between at least two epoxy groups of the sizingagent before or after the sizing agent is covalently bound to thesurface of said carbon fiber.
 2. The method of claim 1, wherein saidepoxy-reactive groups in said crosslinking molecule are selected fromthe group consisting of isocyanate, hydroxy, amino, carboxylic acid,thiol, and amide groups.
 3. The method of claim 1, wherein saidcrosslinking molecule is a sole curing agent used in the method.
 4. Themethod of claim 1, wherein, prior to covalent binding of said sizingagent on the surface of the carbon fiber, said carbon fiber issurface-treated by a process that incorporates on said surface reactivefunctional groups that react with and form covalent bonds with saidsizing agent.
 5. The method of claim 4, wherein said functional groupsare selected from the group consisting of hydroxyl, carboxyl, and aminegroups.
 6. The method of claim 1, wherein a portion of said crosslinkingmolecules are engaged, via less than all of their epoxy-reactive groups,in an equivalent number of covalent bonds with said epoxy groups,wherein said crosslinking molecule possesses at least one freeepoxy-reactive group in addition to the free functional group.
 7. Themethod of claim 6, wherein said at least one free epoxy-reactive groupis an isocyanate group.
 8. A method of making a solid compositecontaining carbon fibers covalently embedded in a polymeric matrix, themethod comprising admixing carbon fibers, having an at least partiallycured epoxy-containing sizing agent covalently bound to their surfaces,with a polymer precursor resin to form a cured polymeric matrix thatcontains said carbon fibers covalently embedded therein, wherein said atleast partially cured epoxy-containing sizing agent contains an epoxyresin possessing epoxy groups engaged in covalent bonds withcrosslinking molecules possessing at least two epoxy-reactive groups andat least one free functional group that crosslinks with functionalgroups of the polymer precursor resin during the curing step, wherein atleast a portion of said crosslinking molecules are engaged, via at leasttwo of their epoxy-reactive groups, in crosslinking bonds between atleast two epoxy groups of the sizing agent.
 9. The method of claim 8,wherein said polymeric matrix is a cured vinyl ester resin.
 10. Themethod of claim 8, wherein said polymeric matrix is a cured unsaturatedpolyester resin.
 11. The method of claim 8, wherein said polymericmatrix is a vinyl addition polymer.
 12. The method of claim 8, whereinsaid epoxy resin is a difunctional or higher functional epoxy resin. 13.The method of claim 8, wherein a portion of said crosslinking moleculesare engaged, via less than all of their epoxy-reactive groups, in anequivalent number of covalent bonds with said epoxy groups, wherein,during said curing step, said crosslinking molecule becomes crosslinkedwith said polymer precursor resin by at least one of its remainingepoxy-reactive groups in addition to becoming crosslinked to saidpolymer precursor resin by the at least one free functional group of thecrosslinking molecule, wherein said polymer precursor resin possessesgroups reactive with said remaining epoxy-reactive groups.
 14. Themethod of claim 13, wherein at least one of said remainingepoxy-reactive groups is an isocyanate group, which is in crosslinkedform with an isocyanate-reactive group of said polymeric matrix.
 15. Themethod of claim 14, wherein said isocyanate-reactive group is selectedfrom the group consisting of hydroxy, carboxylic acid, and epoxy groups.